EP1497299A4 - Kreuzmethathese von direkt mit einer elektronenziehenden gruppe substituierten olefinen unter verwendung von übergangsmetallcarbenkatalysatoren - Google Patents

Kreuzmethathese von direkt mit einer elektronenziehenden gruppe substituierten olefinen unter verwendung von übergangsmetallcarbenkatalysatoren

Info

Publication number
EP1497299A4
EP1497299A4 EP03718252A EP03718252A EP1497299A4 EP 1497299 A4 EP1497299 A4 EP 1497299A4 EP 03718252 A EP03718252 A EP 03718252A EP 03718252 A EP03718252 A EP 03718252A EP 1497299 A4 EP1497299 A4 EP 1497299A4
Authority
EP
European Patent Office
Prior art keywords
substituted
alkyl
aryl
heteroatom
hydrocarbyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03718252A
Other languages
English (en)
French (fr)
Other versions
EP1497299A2 (de
EP1497299B1 (de
Inventor
Robert H Grubbs
John P Morgan
Jennifer A Love
Tina M Trnka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
California Institute of Technology
Original Assignee
California Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by California Institute of Technology filed Critical California Institute of Technology
Publication of EP1497299A2 publication Critical patent/EP1497299A2/de
Publication of EP1497299A4 publication Critical patent/EP1497299A4/de
Application granted granted Critical
Publication of EP1497299B1 publication Critical patent/EP1497299B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • This invention relates generally to a method for carrying out an olefin metathesis reaction using a Group 8 transition metal complex as a catalyst, and more particularly relates to a method for carrying out cross-metathesis reactions using such a catalyst.
  • the invention enables the synthesis of olefins that are directly substituted with an electron- withdrawing group via a cross-metathesis reaction, as reactants to synthesize acrylonitriles as reactants to synthesize disubstituted cyano-olefins.
  • the invention has utility in the fields of catalysis, organic synthesis, and organometallic chemistry.
  • M is a Group 8 transition metal such as ruthenium or osmium
  • X and X' are anionic ligands
  • L and L' are neutral electron donors
  • Such complexes have been disclosed as useful in catalyzing a variety of olefin metathesis reactions, including ring-opening metathesis polymerization (“ROMP”), ring closing metathesis (“RCM”), acyclic diene metathesis polymerization (“ADMET”), ring-opening metathesis (“ROM”), and cross-metathesis (“CM” or “XMET”) reactions.
  • CM cross-metathesis
  • Such metathesis catalysts include those that have been prepared with phosphine ligands, e.g., triphenylphosphine or dimethylphenylphospine, exemplified by phenylmethylene- bis(tricyclohexylphosphine)ruthenium dichloride
  • Trnka and Grubbs (2001), cited supra. These compounds are highly reactive catalysts useful for catalyzing a variety of olefin metathesis reactions, and are tolerant of many different functional groups. See Schwab et al. (1995) Angew. Chem, Int. Ed. Engl. 34:2039-2041 and Schwab et al. (1996) J. Am. Chem. Soc. 118:100-110. However, as has been recognized by those in the field, the compounds display low thermal stability, decomposing at relatively low temperatures. Jafarpour and Nolan (2000) Organometallics 19(11):2055-2057.
  • N-heterocyclic carbene ligands offer many advantages, including readily tunable steric bulk, vastly increased electron donor character, compatibility with a variety of metal species, and improved thermal stability. See Scholl et al.
  • Cy is cyclohexyl
  • Ph is phenyl
  • Mes represents mesityl (2,4,6- trimethylphenyl) .
  • transition metal carbene complexes have been found to address a number of previously unsolved problems in olefin metathesis reactions, particularly cross-metathesis reactions.
  • metathesis reactions with directly functionalized olefins, particularly olefins that are directly substituted with an electron-withdrawing substituent remain a daunting challenge.
  • acrylonitriles are unusually difficult substrates to use in olefin metathesis reactions, and only one single-component catalyst system, based on molybdenum, has been described as active for cyano-olefin cross-metathesis (Crowe et al. (1995) J. Am. Chem. Soc.
  • the present invention is addressed to the aforementioned needs in the art, and provides a novel process for using certain Group 8 transition metal complexes to catalyze olefin metathesis reactions, primarily cross-metathesis reactions, wherein the olefins are substituted with an electron-withdrawing group.
  • the complexes used are metal alkylidene complexes comprised of a Group 8 transition metal, e.g., ruthenium or osmium. These complexes contain, in addition to the functional alkylidene ligand, two anionic ligands and two or three neutral electron donor ligands.
  • One of the neutral electron donor ligands is strongly binding, i.e., selected so as to remain bound to the metal center of the complex throughout the metathesis reaction, while the remaining neutral electron donor ligand(s) are more weakly binding, and thus dissociate from the metal center during reaction, prior to olefin binding.
  • the present complexes allow an olefinic reactant to be substituted with an electron- withdrawing group without significantly compromising the efficiency or selectivity of a metathesis reaction involving that olefin.
  • L 1 is a strongly coordinating neutral electron donor ligand
  • n is zero or 1;
  • L 2 and L 3 are weakly coordinating neutral electron donor ligands
  • X 1 and X 2 are anionic ligands
  • R 1 and R 2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, or may be taken together to form a vinylidene moiety, [00018] wherein any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 can be taken together to form a cyclic group, and further wherein any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 may be attached to a support.
  • Preferred catalysts contain Ru or Os as the Group 8 transition metal, with Ru particularly preferred.
  • the metal centers of these complexes are formally in the +2 oxidation state. It will be appreciated that when n is zero, the metal center has an electron count of 16 and is penta- coordinated, while when n is 1, the metal center has an electron count of 18 and is hexacoordinated.
  • the complexes may also be modified so as to be cationic (in which case one of the anionic ligands dissociates), such that the metal center has an electron count of 14 and is tetracoordinated.
  • X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , and R 2 are as defined previously, r and s are independently zero or 1, t is an integer in the range of zero to 5, Y is any noncoordinating anion, Z 1 and Z 2 are linkages containing 1 to about 6 spacer atoms, any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , Z 1 , Z 2 , R 1 , and R 2 may be taken together to form a cyclic group, e.g., a multidentate ligand, and any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , Z 1 , Z 2 , R 1 , and R 2 may be attached to a support.
  • a multidentate ligand any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , Z 1 , Z 2 , R 1
  • Exemplary catalysts are transition metal carbene complexes wherein L 2 and L 3 are optionally substituted heterocyclic ligands and L 1 is a carbene having the structure of formula (V)
  • X 1 , X 2 , L 1 , L 2 , L 3 , n, R 1 , and R 2 are as defined above; [00024] X and Y are heteroatoms selected from ⁇ , O, S, and P; [00025] p is zero when X is O or S, and p is 1 when X is ⁇ or P; [00026] q is zero when Y is O or S, and q is 1 when Y is N or P; [00027] Q 1 , Q 2 , Q 3 , and Q 4 are independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and -(CO)-, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group; [00028] w, x, y, and z are independently zero or 1; and
  • R 3 , R 3A , R 4 , and R 4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom- containing hydrocarbyl,
  • any two or more of X 1 , X 2 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A , R 4 , and R 4A can be taken together to form a cyclic group, and further wherein any one or more of X 1 , X 2 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A R 4 , and R 4A may be attached to a support.
  • L 1 is an N-heterocyclic carbene having the structure of formula (VII)
  • R 3 and R 4 are defined above, with preferably at least one of R 3 and R 4 , and more preferably both R 3 and R 4 , being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms and/or substituents.
  • Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups.
  • Q is often, although again not necessarily, a two-atom linkage or a three-atom linkage.
  • a preferred metal carbene complex of formula (VI) is a ruthenium complex having the structure of formula (VIII)
  • a method for synthesizing an olefin that is substituted with an electron-withdrawing group and at least one other substitutent, wherein the electron- withdrawing group is directly bound to an olefmic carbon atom involves using a transition metal carbene complex as described above to catalyze a cross-metathesis reaction between two olefmic reactants, or "cross partners," wherein at least one of the olefinic reactants is directly substituted with an electron- withdrawing group E.
  • cross partners wherein at least one of the olefinic reactants is directly substituted with an electron- withdrawing group E.
  • such reactants have the structure of formula (IX)
  • E is the electron-withdrawing group
  • R 5 , R ⁇ , and R 7 are independently selected from the group consisting of hydrogen,
  • Fn is a functional group
  • m is zero or 1;
  • Z is a hydrocarbylene or a substituted and/or heteroatom-containing hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage
  • reaction partner i.e., the second olefinic reactant
  • formula (X) The reaction partner, i.e., the second olefinic reactant, has a molecular structure given by formula (X)
  • R* is a nonhydrogen substituent, e.g., hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or Fn
  • R 8 , R 9 , and R 10 are hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z) m -Fn, or DETAILED DESCRIPTION OF THE INVENTION I. DEFINITIONS AND NOMENCLATURE
  • alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 20 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, ⁇ -propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like.
  • alkyl groups herein contain 1 to about 12 carbon atoms.
  • the term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms
  • the specific term “cycloalkyl” intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms.
  • substituted alkyl refers to alkyl substituted with one or more substituent groups
  • heteroatom-containing alkyl and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom.
  • the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.
  • alkylene refers to a difunctional linear, branched, or cyclic alkyl group, where "alkyl” is as defined above.
  • alkenyl refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 20 carbon atoms containing at least one double bond, such as ethenyl, n- propenyl, isopropenyl, «-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like.
  • Preferred alkenyl groups herein contain 2 to about 12 carbon atoms.
  • lower alkenyl intends an alkenyl group of 2 to 6 carbon atoms
  • specific term “cycloalkenyl” intends a cyclic alkenyl group, preferably having 5 to 8 carbon atoms.
  • substituted alkenyl refers to alkenyl substituted with one or more substituent groups
  • heteroatom-containing alkenyl and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.
  • alkenylene refers to a difunctional linear, branched, or cyclic alkenyl group, where "alkenyl” is as defined above.
  • alkynyl refers to a linear or branched hydrocarbon group of 2 to about 20 carbon atoms containing at least one triple bond, such as ethynyl, «-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkynyl” intends an allcynyl group of 2 to 6 carbon atoms.
  • substituted alkynyl refers to alkynyl substituted with one or more substituent groups
  • heteroatom-containing alkynyl and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom.
  • alkynyl and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.
  • alkoxy intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as -O-alkyl where alkyl is as defined above.
  • a "lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.
  • alkenyloxy and lower alkenyloxy respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage
  • alkynyloxy and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.
  • aryl refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety).
  • Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms.
  • Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like.
  • Substituted aryl refers to an aryl moiety substituted with one or more substituent groups
  • heteroatom- containing aryl and “heteroaryl” refer to aryl substituent, in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.
  • aryloxy refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above.
  • An “aryloxy” group may be represented as -O-aryl where aryl is as defined above.
  • Preferred aryloxy groups contain 5 to 20 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms.
  • Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo- phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy- phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
  • alkaryl refers to an aryl group with an alkyl substituent
  • aralkyl refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above.
  • Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms.
  • Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7- dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-l,4-diene, and the like.
  • aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl- butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4- benzylcyclohexylmethyl, and the like.
  • alkaryloxy and aralkyloxy refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as just defined.
  • acyl refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, or -(CO)-aralkyl
  • acyloxy refers to substituents having the formula -0(CO)-alkyl, -0(CO)-aryl, or -O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as defined above.
  • cyclic refers to alicyclic or aromatic substituents that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic.
  • alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic or polycyclic.
  • halo and halogen are used in the conventional sense to refer to a chloro, bromo, fluoro or iodo substituent.
  • Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like.
  • lower hydrocarbyl intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms
  • hydrocarbylene intends a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species.
  • lower hydrocarbylene intends a hydrocarbylene group of 1 to 6 carbon atoms.
  • Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups
  • heteroatom-containing hydrocarbyl and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom
  • substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups
  • heteroatom-containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom.
  • hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.
  • heteroatom-containing hydrocarbyl group refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
  • heteroalkyl refers to an alkyl substituent that is heteroatom-containing
  • heterocyclic refers to a cyclic substituent that is heteroatom-containing
  • heteroaryl and heteroaromatic respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
  • a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.”
  • substituted as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
  • substituents include, without limitation: functional groups referred to herein as "Fn,” such as halo, hydroxyl, sulfhydryl, C r C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 6 -C 24 alkaryloxy, acyl (including C 2 -C 20 alkylcarbonyl (-CO-alkyl) and C 6 -C 24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C 2 -C 20 alkylcarbonyloxy (-O-CO-alkyl) and C 6 -C 24 arylcarbonyloxy (-O-CO-aryl)), C 2 -C 20 alkoxycarbonyl (-(CO)-O-alkyl), C 6 -C 24 aryloxycarbonyl (-((CO
  • the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
  • the above- mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.
  • substituted appears prior to a list of possible substituted groups, it is intended that the term apply to every member of that group.
  • substituted alkyl, alkenyl, and aryl is to be interpreted as “substituted alkyl, substituted alkenyl, and substituted aryl.”
  • heteroatom-containing appears prior to a list of possible heteroatom-containing groups, it is intended that the term apply to every member of that group.
  • heteroatom-containing alkyl, alkenyl, and aryl is to be interpreted as “heteroatom-containing alkyl, substituted alkenyl, and substituted aryl.”
  • Optional or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not.
  • the phrase “optionally substituted” means that a non- hydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non- hydrogen substituent is not present.
  • M which serves as the transition metal center in the +2 oxidation state, is a Group 8 transition metal, particularly ruthenium or osmium. In a particularly preferred embodiment, M is ruthenium.
  • L 1 is a strongly coordinating neutral electron donor ligand, as will be discussed in detail infra.
  • L 2 and L 3 are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups, and n is zero or 1, such that L 3 may or may not be present.
  • L 2 and L 3 are optionally substituted five- or six-membered monocyclic groups containing 1 to 4, preferably 1 to 3, most preferably 1 to 2 heteroatoms, or are optionally substituted bicyclic or polycylic structures composed of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, it should not be substituted on a coordinating heteroatom, and any one cyclic moiety within a heterocyclic group will generally not be substituted with more than 3 substituents. Examples of L 2 and L 3 include, without limitation:
  • nitrogen-containing heterocycles such as pyridine, bipyridine, pyridazine, pyrimidine, bipyridarnine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H- pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, lH-isoindole, cyclopenta(b)pyridine 3 indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, bisimidazo
  • sulfur-containing heterocycles such as thiophene, 1,2-dithiole, 1,3-dithiole, thiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H- thiopyran, and thioanthrene;
  • oxygen-containing heterocycles such as 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-l-benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen- 1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxan, and dibenzofuran; and
  • mixed heterocycles such as isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-l,2,3-dioxazole, 3H-l,2-oxathiole, 1,3-oxathiole, 4H-l,2-oxazine, 2H-l,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.
  • L 2 and L 3 ligands are aromatic nitrogen-containing and oxygen-containing heterocycles, and particularly preferred L 2 and L 3 ligands are monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3, preferably 1 or 2, substituents.
  • L 2 and L 3 ligands are pyridine and substituted pyridines, such as 3- bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6- dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6- trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4- methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5- dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6- triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichlor
  • any substituents present on L 2 and/or L 3 are selected from halo, C,-C 20 alkyl, substituted C 1 -C 20 alkyl, C r C 20 heteroalkyl, substituted C r C 20 heteroalkyl, C 5 -C 24 aryl, substituted C 5 -C 24 aryl, C 5 -C 24 heteroaryl, substituted C 5 -C 24 heteroaryl, C 6 -C 24 alkaryl, substituted C 6 -C 24 alkaryl, C 6 -C 24 heteroalkaryl, substituted C 6 -C 24 heteroalkaryl, C 6 -C 24 aralkyl, substituted C 6 -C 24 aralkyl, C 6 -C 24 heteroaralkyl, substituted C 6 -C 24 heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C r C 20 alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkylcarbon
  • Preferred substituents on L 2 and L 3 include, without limitation, halo, C r C 12 alkyl, substituted C r C 12 alkyl, C r C 12 heteroalkyl, substituted C r C 12 heteroalkyl, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, C 5 -C 14 heteroaryl, substituted C 5 -C 14 heteroaryl, C 6 -C 16 alkaryl, substituted C 6 -C, 6 alkaryl, C 6 -C 16 heteroalkaryl, substituted C 6 -C I6 heteroalkaryl, C 6 -C 16 aralkyl, substituted C 6 -C 16 aralkyl, C 6 -C 16 heteroaralkyl, substituted C 6 -C 16 heteroaralkyl, C r C 12 alkoxy, C 5 -C 14 aryloxy, C 2 - C 12 alkylcarbonyl, C 6 -C 14 arylcarbonyl
  • substituents are halo, C r C 6 alkyl, C r C 6 haloalkyl, - alkoxy, phenyl, substituted phenyl, formyl, N,N-diC r C 6 alkyl)amino, nitro, and nitrogen heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).
  • L 2 and L 3 may also be taken together to form a bidentate or multidentate ligand containing two or more, generally two, coordinating heteroatoms such as N, O, S, or P, with preferred such ligands being diimine ligands of the Brookhart type.
  • a bidentate or multidentate ligand containing two or more, generally two, coordinating heteroatoms such as N, O, S, or P, with preferred such ligands being diimine ligands of the Brookhart type.
  • One representative bidentate ligand has the structure of formula (XI)
  • R 15 , R 16 , R 17 , and R 18 hydrocarbyl e.g., C,-C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 - C 24 aryl, C 6 -C 24 alkaryl, or C 6 -C 24 aralkyl
  • substituted hydrocarbyl e.g., substituted C t -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, or C 6 -C 24 aralkyl
  • heteroatom- containing hydrocarbyl e.g., C C 20 heteroalkyl, C 5 -C 2 heteroaryl, heteroatom-containing C 6 -C 24 aralkyl, or heteroatom-containing C 6 -C 24 alkaryl
  • substituted heteroatom-containing hydrocarbyl e.g.,
  • X 1 and X 2 are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring.
  • X 1 and X 2 are each independently hydrogen, halide, or one of the following groups: C r C 20 alkyl, C 5 -C 24 aryl, C 1 -C 20 alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 6 -C 24 aryloxycarbonyl, C 2 -C 24 acyl, C 2 -C 24 acyloxy, C r C 20 alkylsulfonato, C 5 -C 24 arylsulfonato, C r C 20 alkylsulfanyl, C 5 -C 24 arylsulfanyl, C r C 20 alkylsulfinyl, or C 5 -C 24
  • X 1 and X 2 may be substituted with one or more moieties selected from C r C 12 alkyl, C,-C 12 alkoxy, C 5 -C 24 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, -Cg alkyl, C r C 6 alkoxy, and phenyl.
  • X 1 and X 2 are halide, benzoate, C 2 -C 6 acyl, C 2 -C 6 alkoxycarbonyl, C,-C 6 alkyl, phenoxy, C,-C 6 alkoxy, C r C 6 alkylsulfanyl, aryl, or C,-C 6 alkylsulfonyl.
  • X 1 and X 2 are each halide, CF 3 C0 2 , CH 3 C0 2 , CFH 2 CO 2; (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane- sulfonate.
  • X 1 and X 2 are each chloride.
  • R 1 and R 2 are independently selected from hydrogen, hydrocarbyl (e.g., C,-C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C r C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl, etc.
  • R 1 and R 2 may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and/or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5 to 8, ring atoms. R 1 and R 2 may also together form a vinylidene moiety or an analog thereof, as discussed infra with respect to catalysts having the structure of formula (II), (III), and (IN).
  • R 1 is hydrogen and R 2 is selected from C r C 20 alkyl, C 2 -C 20 alkenyl, and C 5 -C 24 aryl, more preferably C r C 6 alkyl, C 2 -C 6 alkenyl, and C 5 -C 14 aryl. Still more preferably, R 2 is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from C,-C 6 alkyl, C r C 6 alkoxy, phenyl, and a functional group Fn as defined earlier herein.
  • R 2 is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl.
  • Any two or more (typically two, three, or four) of X 1 , X 2 , L ⁇ L 2 , L 3 , R 1 , and R 2 can be taken together to form a cyclic group, as disclosed, for example, in U.S. Patent No. 5,312,940 to Grubbs et al.
  • cyclic groups may be five- or six-membered rings, or may comprise two or three five- or six- membered rings, which may be either fused or linked.
  • the cyclic groups may be aliphatic or aromatic, and may be heteroatom-containing and/or substituted.
  • the cyclic group may, in some cases, form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.
  • L 1 is a carbene ligand having the structure of formula (V)
  • X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, and q is necessarily zero when Y is O or S.
  • both X and Y are N.
  • Q 1 , Q 2 , Q 3 , and Q 4 are linkers, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and/or heteroatom-containing alkylene) or -(CO)-, and w, x, y, and z are independently zero or 1, meaning that each linker is optional. Preferably, w, x, y, and z are all zero. Further, two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group.
  • linkers e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and/or heteroatom-containing alkylene) or -(CO)-
  • w, x, y, and z are independently zero or 1, meaning that each linker is optional.
  • R 3 , R 3A R 4 , and R 4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom- containing hydrocarbyl.
  • any two or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A , R 4 , and R 4A can be taken together to form a cyclic group, and any one or more of X 1 , X 2 , L 1 , L 2 , L 3 , R 1 , R 2 , R 3 , R 3A R 4 , and R 4A may be attached to a support.
  • R 3A and R A are linked to form a cyclic group so that the carbene ligand has the structure of formula (VII)
  • R 3 and R 4 are defined above, with preferably at least one of R 3 and R 4 , and more preferably both R 3 and R 4 , being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms and/or substituents.
  • Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups.
  • Q is often, although again not necessarily, a two-atom linkage or a three-atom linkage.
  • Examples of N-heterocyclic carbene ligands suitable as L 1 thus include, but are not limited to, the following:
  • Examples of functional groups here include carboxyl, C J - Q alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 5 -C 24 alkoxycarbonyl, C 2 -C 24 acyloxy, C r C 20 alkylthio, C 5 -C 24 arylthio, C,-C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, optionally substituted with one or more moieties selected from C r C 12 alkyl, C r C 12 alkoxy, C 5 -C 14 aryl, hydroxyl, sulfhydryl, formyl, and halide.
  • R 11 , R 12 , R 13 , and R 14 are preferably independently selected from hydrogen, C r C, 2 alkyl, substituted C,-C 12 alkyl, C r C 12 heteroalkyl, substituted C C 12 heteroalkyl, phenyl, and substituted phenyl.
  • any two of R 11 , R 12 , R 13 , and R 14 may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C 4 -C 12 alicyclic group or a C 5 or C 6 aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents.
  • R 3 and R 4 are aromatic, they are typically although not necessarily composed of one or two aromatic rings, which may or may not be substituted, e.g., R 3 and R 4 may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like.
  • R 3 and R 4 are the same and are each unsubstituted phenyl or phenyl substituted with up to three substituents selected from C r C 20 alkyl, substituted C,-C 20 alkyl, - o heteroalkyl, substituted C r C 20 heteroalkyl, C 5 -C 24 aryl, substituted C 5 -C 2 aryl, C 5 -C 24 heteroaryl, C 6 -C 24 aralkyl, C 6 -C 24 alkaryl, or halide.
  • any substituents present are hydrogen, C,-C 12 alkyl, C r C 12 alkoxy, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, or halide. More preferably, R 3 and R 4 are mesityl.
  • Examples of such catalysts include, but are not limited to, the following:
  • Ph represents phenyl
  • Mes represents mesityl
  • Additional transition metal carbene complexes include, but are not limited to:
  • suitable solid supports may be of synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic. Attachment to the support will generally, although not necessarily, be covalent, and the covalent linkage may be direct or indirect, if indirect, typically through a functional group on a support surface.
  • transition metal complexes used as catalysts herein can be prepared by several different methods, such as those described by Schwab et al. (1996) J. Am. Chem. Soc. 118:100- 110, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749- 750, U.S. Patent No. 5,312,940 and U.S. Patent No. 5,342,909. Also see U.S. Patent Publication No. 2003/0055262 to Grubbs et al.
  • the transition metal complexes described in the foregoing section are used herein to catalyze an olefin metathesis reaction to synthesize olefins directly substituted with an electron- withdrawing group and substituted with at least one additional substituent.
  • the first olefinic reactant has the structure of formula (IX)
  • E is an electron-withdrawing group, which, as will be appreciated by those of ordinary skill in the art, is a group that has greater electronegativity than the carbon atom to which it is bound. In general, this means that E is more electron-withdrawing than a hydrogen atom.
  • representative electron- withdrawing substituents include, without limitation, halo, cyano, C r C 20 haloalkyl (preferably C r C 12 haloalkyl, more preferably C,-C 6 haloalkyl), C ⁇ -C 20 alkylsulfonyl (preferably C r C 12 alkylsulfonyl, more preferably C r C 6 alkylsulfonyl), C 5 -C 24 arylsulfonyl (preferably C 5 -C 14 arylsulfonyl), carboxyl, C 5 -C 24 aryloxy (preferably C 5 -C 14 aryloxy), C,-C 20 alkoxy (preferably C r C 12 alkoxy, more preferably C r C 6 alkoxy), C 6 -C 24 aryloxy), C r C 20 alkoxy (preferably C,-C 12 alkoxy, more preferably C r C 6 alkoxy), C 6 -C 24 aryloxy),
  • R 5 , R 6 , and R 7 are independently selected from the group consisting of hydrogen, [000101] -(Z) m -Fn, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, and, if substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein one or more of the substituents may be -(Z) m -Fn.
  • R 5 is hydrogen or substituted and/or heteroatom-containing C,-C 12 hydrocarbyl, e.g., C ⁇ -C 12 alkyl, substituted C r C 12 alkyl, -C ⁇ heteroalkyl, substituted C r C 12 heteroalkyl, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, C 5 -C 14 heteroaryl, substituted C 5 -C, 4 heteroaryl, C 6 -C 16 alkaryl, substituted C 6 -C 16 alkaryl, C 6 -C 16 heteroalkaryl, substituted C 6 -C 16 heteroalkaryl, C 6 -C 16 aralkyl, substituted C 6 -C 16 aralkyl, C 6 -C 16 heteroaralkyl, or substituted C 6 -C 16 heteroaralkyl, and R 6 and R 7 are hydrogen.
  • R 5 is hydrogen, C,-C 12 alkyl, or C 6
  • Fn is a functional group as defined earlier herein, with exemplary Fn groups including, without limitation, halide, hydroxyl, sulfhydryl, 0,-0, 0 alkoxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 2 -C 20 alkylcarbonyl, C 6 -C 24 arylcarbonyl, C 2 -C 20 alkylcarbonyloxy, C 6 -C 24 arylcarbonyloxy, C 2 -C 20 alkoxycarbonyl, C 6 -C 24 aryloxycarbonyl, halocarbonyl, C 2 -C 20 alkylcarbonato, C 6 -C 24 arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C r C 20 alkyl)- substituted carbamoyl, di-(C,-C 20 alkyl)-substituted carbamoyl, di-N-
  • Zis a hydrocarbylene e.g., C r C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 - C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene
  • substituted hydrocarbylene e.g., substituted C r C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene
  • heteroatom-containing hydrocarbylene e.g., C r C 20 heteroalkylene, C 2 -C 20 heteroalkenylene, C 2 -C 20 heteroalkynylene, C 5 -C 24 heteroarylene, heteroatom-containing C 6 -C 24 aralkylene, or heteroatom-containing C 6 -C 24 alkarylene
  • Preferred Z linkages are C,-C 12 alkylene, optionally substituted and/or heteroatom-containing, and particularly preferred Z linkages are C C 6 alkylene.
  • the functional group will generally not be directly bound to the olefinic carbon through a heteroatom containing one or more lone pairs of electrons, e.g., an oxygen, sulfur, nitrogen or phosphorus atom; with such functional groups, there will normally be an intervening linkage Z, i.e., m is 1.
  • reaction partner i.e., the second olefinic reactant
  • formula (X) The reaction partner, i.e., the second olefinic reactant, has a molecular structure given by formula (X)
  • R* is a nonhydrogen substituent, e.g., hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, or Fn
  • R 8 , R 9 , and R 10 are hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z) m -Fn, or -(J) w -R*.
  • R 8 and R 10 are hydrogen, or (2) R s and R 9 are hydrogen and R 10 is either hydrogen or -(J) w -R*;
  • J is C r C 6 alkylene, substituted C r C 6 alkylene, C r C 6 heteroalkylene, or substituted C r C 6 heteroalkylene, and is preferably C,-C 6 alkylene;
  • R* is selected from C r C 20 alkyl, substituted C r C 20 alkyl, C r C 20 heteroalkyl, substituted -Gy, heteroalkyl, C 5 -C 24 aryl, substituted C 5 -C 24 aryl, C 5 -C 24 heteroaryl, substituted C 5 -C 2 heteroaryl, C 6 -C 24 aralkyl, substituted C 6 -C 24 aralkyl, C 6 -C 24 heteroaralkyl, and substituted C 6 -C 24 heteroaralkyl, hydroxyl, sulfhydryl, protected hydroxyl, protected sulfhydryl, C,-C 20 alkoxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 2 -C 20 alkylcarbonyl, C 6 -C 24 arylcarbonyl, C 2 -C 20 alkylcarbonyloxy, C 6 -C 24 arylcarbony
  • J is C r C 3 alkylene, e.g., methylene
  • R* is selected from hydroxyl, sulfhydryl, protected hydroxyl, protected sulfhydryl, C r C 12 alkoxy, C 5 - C 14 aryloxy, C 6 -C 14 aralkyloxy, C 2 -C 12 alkylcarbonyl, C 6 -C I4 arylcarbonyl, C 2 -C 12 alkylcarbonyloxy, C 6 -C 14 arylcarbonyloxy, C 2 -C 12 alkoxycarbonyl, C 6 -C 14 aryloxycarbonyl, halocarbonyl, di-(C r C 12 alkyl)-substituted carbamoyl, di-N-(C,-C 12 alkyl)-N-(C 5 -C w aryl)- substituted carbamoyl, mono-(C 5 -
  • R* substituents are hydroxyl, protected hydroxyl, C,-C 6 alkoxy, C 5 - C 14 aryloxy, C 6 -C 14 aralkyloxy, C 2 -C 6 alkylcarbonyl, C 6 -C 14 arylcarbonyl, halocarbonyl, formyl, di-(C r C 6 alkyl)-substituted amino, di-(C 5 -C, 4 aryl)-substituted amino, C,-C 6 alkylthio, and C 5 -C 14 arylthio.
  • the CM reaction will generally be carried out in a solvent at a temperature in the range of about 20°C to about 80°C, optimally about 25°C to about 45°C, with about 0.1 mol% to about 5 mol%, optimally about 0.5 mol% to about 3.5 mol% catalyst. It should be noted that depending on the substitution of the pyridine ligands, high Z-olefin selectivity (> 10:1 Z:E) also can be achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
EP03718252A 2002-04-05 2003-04-07 Kreuzmethathese von direkt mit einer elektronenziehenden gruppe substituierten olefinen unter verwendung von übergangsmetallcarbenkatalysatoren Expired - Lifetime EP1497299B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US37030802P 2002-04-05 2002-04-05
US370308P 2002-04-05
PCT/US2003/010694 WO2003087167A2 (en) 2002-04-05 2003-04-07 Cross-metathesis of olefins directly substituted with an electron-withdrawing group using transition metal carbene catalysts

Publications (3)

Publication Number Publication Date
EP1497299A2 EP1497299A2 (de) 2005-01-19
EP1497299A4 true EP1497299A4 (de) 2006-08-02
EP1497299B1 EP1497299B1 (de) 2012-06-27

Family

ID=29250513

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03718252A Expired - Lifetime EP1497299B1 (de) 2002-04-05 2003-04-07 Kreuzmethathese von direkt mit einer elektronenziehenden gruppe substituierten olefinen unter verwendung von übergangsmetallcarbenkatalysatoren

Country Status (5)

Country Link
US (1) US7598330B2 (de)
EP (1) EP1497299B1 (de)
CN (1) CN1659172B (de)
AU (1) AU2003221674A1 (de)
WO (1) WO2003087167A2 (de)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2512815A1 (en) * 2003-01-13 2004-07-29 Cargill, Incorporated Method for making industrial chemicals
US7094898B2 (en) * 2003-05-29 2006-08-22 University Of Ottawa Ruthenium compounds, their production and use
EP1648943B1 (de) * 2003-07-28 2010-03-31 Firestone Polymers, LLC Entfernen von gelartigen ungesättigten elastomeren aus der polymerisationsapparatur, die mit deren herstellung verbunden ist.
US8058351B2 (en) * 2005-05-20 2011-11-15 Bridgestone Corporation Method for preparing low molecular weight polymers
WO2007081987A2 (en) * 2006-01-10 2007-07-19 Elevance Renewable Sciences, Inc. Method of making hydrogenated metathesis products
EP2046719B1 (de) 2006-07-12 2013-09-04 Elevance Renewable Sciences, Inc. Ringöffnungs-kreuzmetathese zyklischer olefine mit samenölen und dergleichen
WO2008010961A2 (en) 2006-07-13 2008-01-24 Elevance Renewable Sciences, Inc. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis
WO2008048520A2 (en) 2006-10-13 2008-04-24 Elevance Renewable Sciences, Inc. Methods of making organic compounds by metathesis and hydrocyanation
CN102123979A (zh) 2006-10-13 2011-07-13 埃莱文斯可更新科学公司 通过烯烃复分解由内烯烃合成末端烯烃的方法
CN101558027B (zh) * 2006-10-13 2013-10-16 埃莱文斯可更新科学公司 通过复分解反应制备α，ω-二羧酸烯烃衍生物的方法
CN101594937B (zh) * 2006-11-21 2014-04-30 加州理工学院 含有亚噻唑-2-基配体的烯烃复分解反应引发剂
DE102007039695A1 (de) 2007-08-22 2009-02-26 Lanxess Deutschland Gmbh Katalysatoren für Metathese-Reaktionen
DE102007039525A1 (de) 2007-08-21 2009-02-26 Lanxess Deutschland Gmbh Verfahren zum Metathese-Abbau von Nitrilkautschuk
EP2027920B1 (de) 2007-08-21 2014-10-08 LANXESS Deutschland GmbH Katalysatoren für Metathese-Reaktionen
DE102007039526A1 (de) 2007-08-21 2009-02-26 Lanxess Deutschland Gmbh Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen
DE602007006480D1 (de) * 2007-08-21 2010-06-24 Lanxess Deutschland Gmbh Metathese eines Nitrilkautschuks in Gegenwart von Übergangsmetallkomplexkatalysatoren
EP2147721A1 (de) 2008-07-08 2010-01-27 Lanxess Deutschland GmbH Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen
EP2143489A1 (de) * 2008-07-08 2010-01-13 Lanxess Deutschland GmbH Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen
CN102159603B (zh) * 2008-08-04 2014-05-07 费尔斯通聚合物有限责任公司 易位聚合物的加合物及其制备方法
EA020900B1 (ru) 2009-05-05 2015-02-27 Стипэн Компани Композиция для добычи нефти, способ добычи нефти из нефтеносного пласта и сульфонированное производное внутренних олефинов
CA2771242A1 (en) 2009-08-31 2011-03-03 Lanxess Deutschland Gmbh Vulcanizable polymer composition comprising a low molecular weight optionally hydrogenated nitrile rubber
EP2289623A1 (de) 2009-08-31 2011-03-02 LANXESS Deutschland GmbH Metathese eines Nitrilkautschuks in Gegenwart von Übergangsmetallkatalysatoren
EP2289620A1 (de) 2009-08-31 2011-03-02 LANXESS Deutschland GmbH Verfahren zur Herstellung von hydriertem Nitrilgummi
EP2506972B1 (de) * 2009-12-03 2019-04-17 Umicore AG & Co. KG Geträgerte olefinmetathesekatalysatoren
EP2395034A1 (de) 2010-06-14 2011-12-14 LANXESS Deutschland GmbH Blends aus teilhydriertem Nitrilkautschuk und Silikonkautschuk, darauf basierende vulkanisierbaren Mischungen und Vulkanisate
EP2418225A1 (de) 2010-08-09 2012-02-15 LANXESS Deutschland GmbH Teilhydrierte Nitrilkautschuke
US9597674B2 (en) * 2011-01-14 2017-03-21 California Institute Of Technology Z-selective olefin metathesis catalysts and their synthetic procedure
EP2484700B1 (de) 2011-02-04 2013-10-09 LANXESS Deutschland GmbH Funktionalisierte Nitrilkautschuke und ihre Herstellung
MX352266B (es) * 2011-09-14 2017-11-16 Materia Inc Mejora de las cubiertas de celdas electrolíticas que comprende una composición de resina polimerizada con un catalizador de metátesis de olefina del grupo 8.
WO2013056461A1 (en) 2011-10-21 2013-04-25 Lanxess Deutschland Gmbh Catalyst compositions and their use for hydrogenation of nitrile rubber
WO2013056459A1 (en) 2011-10-21 2013-04-25 Lanxess Deutschland Gmbh Catalyst compositions and their use for hydrogenation of nitrile rubber
WO2013098056A1 (en) 2011-12-28 2013-07-04 Lanxess Deutschland Gmbh Purification of optionally hydrogenated nitrile rubber
WO2013098052A2 (en) 2011-12-28 2013-07-04 Lanxess Deutschland Gmbh Metathesis of nitrile rubbers in the presence of transition metal complex catalysts
WO2014093687A1 (en) 2012-12-12 2014-06-19 California Institute Of Technology Z-selective metathesis catalysts

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US611121A (en) * 1898-09-20 Grain-bagging machine
EP1253156A3 (de) * 1992-04-03 2004-01-07 California Institute Of Technology Hochwirksame Ruthenium- oder Osmium- Metall-Carben-Komplexe für Olefinmetathesereaktionen, und deren Herstellung und Verwendung
US5312940A (en) * 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
US5831108A (en) * 1995-08-03 1998-11-03 California Institute Of Technology High metathesis activity ruthenium and osmium metal carbene complexes
WO2000043343A2 (en) * 1999-01-26 2000-07-27 California Institute Of Technology Novel methods for cross-metathesis of terminal olefins
WO2002079126A1 (en) * 2001-03-30 2002-10-10 California Institute Of Technology Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts
CA2455893C (en) 2001-08-01 2011-01-18 California Institute Of Technology Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BLANCO, O. M. ET AL: "New results on the functionalization of terminal alkenes by cross -metathesis reactions", SYNLETT , (5), 557-558 CODEN: SYNLES; ISSN: 0936-5214, 1999, XP002385502 *
CHATTERJEE, A. K. ET AL: "Synthesis of Trisubstituted Alkenes via Olefin Cross- Metathesis", ORGANIC LETTERS , 1(11), 1751-1753 CODEN: ORLEF7; ISSN: 1523-7060, 1999, XP002385503 *
LOVE, J. A. ET AL: "A practical and highly active ruthenium-based catalyst that effects the cross metathesis of acrylonitrile", ANGEWANDTE CHEMIE, INTERNATIONAL EDITION , 41(21), 4035-4037 CODEN: ACIEF5; ISSN: 1433-7851, 4 November 2002 (2002-11-04), XP002385504 *
See also references of WO03087167A2 *

Also Published As

Publication number Publication date
CN1659172B (zh) 2012-08-01
US20030236427A1 (en) 2003-12-25
WO2003087167A3 (en) 2003-12-11
EP1497299A2 (de) 2005-01-19
EP1497299B1 (de) 2012-06-27
CN1659172A (zh) 2005-08-24
WO2003087167A2 (en) 2003-10-23
US7598330B2 (en) 2009-10-06
AU2003221674A1 (en) 2003-10-27
AU2003221674A8 (en) 2003-10-27

Similar Documents

Publication Publication Date Title
EP1497299B1 (de) Kreuzmethathese von direkt mit einer elektronenziehenden gruppe substituierten olefinen unter verwendung von übergangsmetallcarbenkatalysatoren
EP1735352B1 (de) Einen n-heterocyclischen carbenliganden enthaltende latente katalysatoren mit hoher aktivität für die olefinmetathese
JP4922558B2 (ja) 環状オレフィンモノマーの環挿入重合による大環状ポリマーの合成
AU2005252276B2 (en) Transition metal carbene complexes containing a cationic substituent as catalysts of olefin metathesis reactions
EP3164409B1 (de) Gruppe-8-übergangsmetallkatalysatoren und verfahren zur herstellung davon und verfahren zur verwendung davon in der metathesereaktion
US9427731B2 (en) Supported olefin metathesis catalysts
WO2010021740A1 (en) Telechelic olefin metathesis polymers from renewable feedstocks
JP2005534777A5 (de)
WO2011119778A2 (en) Method for in-situ formation of metathesis catalysts
EP4194092A1 (de) Synthese und charakterisierung von metathesekatalysatoren
EP3496855A1 (de) Metathesekatalysatoren
EP2984055B1 (de) Herstellung von tensiden mittels kreuzmethathese
US20200369697A1 (en) Molybdenum oxo alkylidene compounds, methods of making the same and use thereof in metathesis reactions
EP3515885B1 (de) Herstellung von aminosäuren und aminosäurederivaten
AU2011205218B2 (en) Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand
CN101090915A (zh) 含有n－杂环卡宾配体的潜伏的高活性烯烃置换催化剂

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041022

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TRNKA, TINA, M.

Inventor name: LOVE, JENNIFER, A.

Inventor name: GRUBBS, ROBERT, H.

Inventor name: MORGAN, JOHN, P.

RIN1 Information on inventor provided before grant (corrected)

Inventor name: GRUBBS, ROBERT, H.

Inventor name: TRNKA, TINA, M.

Inventor name: LOVE, JENNIFER, A.

Inventor name: MORGAN, JOHN, P.

A4 Supplementary search report drawn up and despatched

Effective date: 20060704

17Q First examination report despatched

Effective date: 20070330

RIN1 Information on inventor provided before grant (corrected)

Inventor name: MORGAN, JOHN, P.

Inventor name: TRNKA, TINA, M.

Inventor name: GRUBBS, ROBERT, H.

Inventor name: LOVE, JENNIFER, A.

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 564170

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120715

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60341390

Country of ref document: DE

Effective date: 20120830

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20120627

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 564170

Country of ref document: AT

Kind code of ref document: T

Effective date: 20120627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120928

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121029

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20121008

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20130328

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60341390

Country of ref document: DE

Effective date: 20130328

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120927

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130407

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130407

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20030407

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60341390

Country of ref document: DE

Representative=s name: D YOUNG & CO LLP, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20220303

Year of fee payment: 20

Ref country code: CH

Payment date: 20220314

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20220308

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20220302

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60341390

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20230406

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20230406